DE10227850A1 - Circuit element, useful as memory, comprises a monomolecular layer of redox-active bis-pyridinium molecules situated between conductive layers - Google Patents

Abstract

A circuit element comprises a monomolecular layer of redox-active bis-pyridinium molecules situated between the first and second conductive layers, whereby the bis-pyridinium molecules of the monomolecular layer are immobilized on the electrically conductive layer as at least one discrete region. A circuit element (I) comprises a first layer of an electrically insulating substrate material with a first electrically conductive material comprising at least one discrete region that is embedded into or applied onto the substrate; a second layer with a second electrically conductive material and a monomolecular layer of redox-active bis-pyridinium molecules situated between the first and second layers, whereby the bis-pyridinium molecules of the monomolecular layer are immobilized on the electrically conductive layer as at least one discrete region and are in electrical contact with the second electrical material of the second layer and electrically inert molecules are immobilized on the first layer to form a matrix that surrounds at least one discrete region of the monomolecular layer of bispyridinium molecules. Independent claims are included for: (1) a process for the production of a circuit element (I) by application and/or embedding of a first electrically conductive material to at least one discrete position on/in the substrate material; immobilization of a monomolecular layer of redox-active bispyridinium molecules onto at least one discrete region of the first electrically conductive material; immobilization of electrically inert molecules onto the first layer of electrically insulating material that surround at least one region with the monomolecular layer of bis-pyridinium molecules; application of a second layer with a second electrically conductive material onto the layer of the electrically inert molecules and the bis-pyridinium molecules, whereby the bispyridinium molecules of the monomolecular layer are in contact with the second electrically material of the second layer; (2) bispyridinium compounds of formula (1) with the exclusion of N,N'-dimethyl-4,6,9,10-tetrahydro-2,7-diazapyreniumdiiodide; 1,1',2,2'-tetramethyl-4,4'-bispyridinium; 1,1',2-trimethyl-4,4'-bispyridinium; N,N'-dimethyl-2,7-diazapyrenium; N-methyl-N'-(p-toloyl)-2,7-diazapyrenium, 1,1'-dimethyl-2-phenyl-6-(p-toloyl)-4,4'-bispyridium diperchlorate; 1,1'-dimethyl-2-phenyl-4,4'-bispyridium diperchlorate; 6-(phenyl)-1,1',2-trimethyl-4,4'-bispyridium diperchlorate; 6-(phenyl)-1,1',2-trimethyl-4,4'-bispyridium diperchlorate or 1,1'-dimethyl-2-phenyl-6-(2,5-dichloro-3-thienyl)-4,4'-bispyridiumdiperchlorate. (1) Xa, XbS, N or O; Ra, Rbalkyl, aryl, alkylaryl, alkenyl, halogen, CN, OCN, COOH, COOR1>, CONHR1>, NO2, OH, OR1>, NH2, NHR1>, NR'R, SH or SR1>; R'R : alkyl, aryl, alkylaryl, alkenyl or alkinyl or Ra and Rb together form a bridge between the two aromatic ring systems comprising 1-3 atoms of C, S, N or O bonded by single, double or triple bonds and optionally substituted by Re; RcR a and Rb; Y : CH2, O, S, NH, NR1>, COO, CONH, CHCH, CC or aryl; Aa, ZbCH3, -CHCH2, SH, -SS-, SiCl3, Si(OR)3, SiR(OR')(OR), SiR(OR')2, Si(R'R)NH2, Si(R'2)NH2, COOH, SO3, PO3H or NH2; n, q : 0-12; j, k : 0-6; p., m : 0-12.

Description

The invention relates to a circuit element with a first layer of an electrically insulating substrate material, Method of manufacturing a circuit element, bispyridinium compounds and their use in circuit elements.

The conventional one on silicon components such as CMOS chips (CMOS: complementary metal-oxide-semiconductor), based microelectronics, is also becoming more progressive Miniaturization reaching its limits. As one of the possible Molecular electronics is becoming a way of further downsizing components discussed.

In addition to the general problem, To develop circuit elements with the help of molecular electronics, is another aspect considered in this context, the Development of alternatives to the previous semiconductor memory elements such as DRAMs (dynamic random access memories), SRAMs (static random access memories) or flash memory.

From [1] it is known that with the help configurable from monomolecular layers based on rotaxanes Circuit elements can be obtained for construction of logic gates can be used. The basis for this is that the monomolecular layers of rotaxanes from a conductive in a less conductive brought by applying a voltage, i.e. Can be "switched". However this switching process known from [1] is irreversible and thus for one Write once / mulitple read application suitable.

From [2] it is known that with the help another special class of molecules, the so-called catenanes, a reversible switching process can be. However, this switching process will be significantly smaller Signals observed.

The two known from [1) and [2] Circuit elements, however, have other disadvantages for a wide range practical application. For one, rotaxanes and catenanes are only through elaborate Syntheses available. On the other hand, both circuit elements are used for generation of the monomolecular layers Langmuir-Blodgett method applied. About that In addition, the suitability of these Langmuir-Blodgett processes for coating surfaces of Components such as silicon wafers that are commonly used in manufacturing serve electrical components, still uncertain.

In addition to the approaches to Development of circuit elements based on organic molecular layers is known from [3] that the special combination of a molecule with a bispyridinium unit and a nanoparticle (metal cluster) made of gold is an electrical one Switch can be realized. Since nanotechnology is still in its infancy, it is questionable whether this system in the foreseeable future for practical use can be used.

The invention is based on the problem alternative electrical circuit elements and methods for their To provide manufacturing.

The problem is caused by the circuit element as well as the method with the features according to the independent claims.

Such a circuit element is a circuit element with a first layer of an electrical insulating substrate material and with a first electrically conductive material. This first electrically conductive Material is designed as at least one discrete area, that it is embedded in the substrate material and / or on the substrate material is applied.

The circuit element also has a second layer with a second electrically conductive material on and a monomolecular layer of redox-active bispyridinium molecules that between the first layer of the electrically insulating substrate material and the second layer with the second electrically conductive material is arranged. The bispyridinium molecules are the monomolecular ones Layer on the electrically conductive immobilized as at least one discrete area formed material. The bispyridinium molecules are in the monomolecular layer further with the second electrical material of the second layer in electrical contact.

Furthermore, the circuit element on the first layer of the electrically insulating substrate material electrically inert molecules immobilized, which form a matrix, the at least one discrete area with the monomolecular layer of bispyridinium molecules surrounds.

A redox-active bispyridinium molecule or a redox-active bispyridinium compound is understood here to mean a chemical compound which can reversibly accept and release electrons, ie, chemically speaking, can change their oxidation state by reduction and oxidation, and a bispyridinium unit (see. 1 . 2 ) serves as the electron acceptor or electron donor. In this redox process of the bispyridinium unit or group, which is also known under the abbreviation "bipy", this is either present as a double positively charged cation or after electron uptake as a single positively charged radical cation. This redox process can be carried out using the reaction equation bipy ^{2 +} + e ^- ↔ bipy ⁺ describe.

In general, any Ver can be used as a functional unit in a circuit element described here use bond with one or more bispyridinium units, which can reverse the two oxidation states described above.

wobei in Formel (I)
eines oder mehrere der Kohlenstoffatome der beiden aromatischen Ringssysteme der Bispyridinium-Einheit unabhängig voneinander durch (mindestens) eine Gruppierung X_a bzw. X_b ersetzt sein kann, die jeweils für ein Heteroatom steht, das aus S, N und O ausgewählt wird, oder für eine Leerstelle steht (d.h. wodurch ein 5-Ring erzeugt wird)
eines oder mehrere der Kohlenstoffatome der beiden Ringssysteme jeweils unabhängig voneinander einen Substituenten R_a bzw. R_b aufweisen kann, der jeweils unabhängig für Alkyl, Aryl, Alkylaryl, Alkenyl, Alkinyl, Halogen, CN, OCN, NCO, COOH, COOR', CONHR', NO₂, OH, OR', NH₂, NHR', NR'R'', SH und SR' steht, wobei R' und R'' unabhängig voneinander Alkyl, Aryl, Alkylaryl, Alkenyl oder Alkinyl sein kann, oder
wobei R_a und R_b zusammen eine Verbrückung zwischen den beiden aromatischen Ringsystemen bilden kann, die 1 bis 3 Atome umfasst, wobei die Atome unabhängig voneinander aus C, S, N und O ausgewählt werden und durch eine Einfach-, Doppel- oder Dreifachbindung miteinander verknüpft sein können und ferner einen Substituenten R_c aufweisen können, wobei der Substituent R_c die für R_a und R_b oben angegebene Bedeutung hat,
Y für eine Gruppe steht, die unabhängig voneinander aus CH₂, O, S, NH, NR', COO, CONH, CH=CH, C=C oder Aryl ausgewählt werden kann,
Z_a und Z_b unabhängig voneinander jeweils CH₃, -CH=CH₂, SH, -S-S-, -S(CO)-CH₃, SiCl₃, Si(OR)₃, SiR(OR')(OR''), SiR(OR')₂, Si(R'R'')NH₂, COOH, SO₃, PO₃H, oder NH₂ sein kann, wobei R' und R" jeweils unabhängig voneinander Alkyl, Aryl, Arylalkyl, Alkenyl oder Alkinyl sein kann,
wobei n, q jeweils unabhängig voneinander einen Wert zwischen 0 und 12 annehmen können,
j und k jeweils unabhängig voneinander einen Wert zwischen 0 und 6 annehmen können,
p und m jeweils unabhängig voneinander einen Wert zwischen 0 und 12 annehmen können.In a preferred embodiment, these bispyridinium molecules are compounds of the general formula (I)

where in formula (I)
one or more of the carbon atoms of the two aromatic ring systems of the bispyridinium unit can be replaced independently of one another by (at least) one group X _a or X _b , each of which represents a hetero atom selected from S, N and O, or for there is an empty space (ie creating a 5-ring)
one or more of the carbon atoms of the two ring systems can each independently have a substituent R _a or R _b , each of which is independently for alkyl, aryl, alkylaryl, alkenyl, alkynyl, halogen, CN, OCN, NCO, COOH, COOR ', CONHR ', NO ₂ , OH, OR', NH ₂ , NHR ', NR'R'', SH and SR', where R 'and R''can independently be alkyl, aryl, alkylaryl, alkenyl or alkynyl, or
where R _a and R _b together can form a bridge between the two aromatic ring systems, which comprises 1 to 3 atoms, the atoms being selected independently of one another from C, S, N and O and by a single, double or triple bond with one another may be linked and may also have a substituent R _c , where the substituent R _{c has} the meaning given above for R _a and R _b ,
Y represents a group which can be selected independently of one another from CH ₂ , O, S, NH, NR ', COO, CONH, CH = CH, C = C or aryl,
Z _a and Z _b independently of one another each CH ₃ , -CH = CH ₂ , SH, -SS-, -S (CO) -CH ₃ , SiCl ₃ , Si (OR) ₃ , SiR (OR ') (OR'' ), SiR (OR ') ₂ , Si (R'R'') NH ₂ , COOH, SO ₃ , PO ₃ H, or NH ₂ , where R' and R "are each independently alkyl, aryl, arylalkyl, Can be alkenyl or alkynyl,
where n, q can independently assume a value between 0 and 12,
j and k can each independently have a value between 0 and 6,
p and m can each independently assume a value between 0 and 12.

Connections are preferred in which the bonded to the nitrogen atom of the respective ring Chain has no more than 20 atoms in total. there Again, compounds are preferred in which both are combined Chains together a total length of more than 30 atoms. Expressed using the indices means this that (j · q + p) or (k · n + m) preferably each independently a value (integer) not greater than 20 are assumed. The sum of (jq + p) + (kn + m) is preferably not larger than 30. For the sake of clarity it should be emphasized here that group Z is not considered in this way the chain length of the two substituents attached to the N atoms is taken into account (see the detailed definition of Z below).

Since the bispyridinium compounds used here are generally in cationic form, the bispyridinium compounds are used in the form of their suitable salts. Suitable counter-ions are, for example, the hydroxide anion (OH ^- ), the anions of the halides, in particular Br ^- and Cl ^- , anions of organic acids such as acetate or complex anions such as the PF ₆ ^- anion, or other complex anions such as that Anions of strong acids such as NO ₃ ^- , ClO ₄ ^- , or SO ₄ ^2– . Further examples of suitable anions are complex anions such as BF ₄ ^- , CF ₃ SO ₃ ^- (triflate), B (Ph) ₄ ^- or complex metal anions such as [PtC1 ₄ ] ^2– .

Alkyl groups can be those described here Compounds of formula (I) or (II) straight-chain or branched, be substituted or unsubstituted. This also applies if they occur in other groups, e.g. in alkoxy, alkylmercapto, Alkoxycarbonyl groups. Alkyl groups with 1 to 12 are preferred Carbon atoms and particularly preferred are alkyl groups with 1 to 8 carbon atoms, especially in the compounds of the formula (I). The term alkyl also includes cycloalkyl groups with 3 to 8 ring carbon atoms, which are also substituted or unsubstituted could be.

Alkenyl and alkynyl groups in the Compounds of formula (I) or (II) can also be straight chain or be branched, substituted or unsubstituted. This is also true if they occur in other groups, e.g. in alkoxy, alkylmercapto, Alkoxycarbonyl groups. Alkenyl or alkynyl groups having 2 to 12 carbon atoms are preferred and particularly preferred are alkenyl or alkynyl groups with 2 up to 8 carbon atoms, especially in the compounds of the formula (I). The term alkenyl also includes cycloalkyenyl groups 3 to 8 ring carbon atoms, which are also substituted or unsubstituted could be.

A preferred substituent here the alkyl alkenyl or alkynyl group is halogen, i.e. Fluorine, Chlorine, bromine or iodine, with fluorine being particularly preferred.

If R _a and R _b together form a bridge between the two ring systems of the compounds of the formula (I), it should be emphasized at this point that in this case an HC = CH group is a preferred alkenyl group, which is preferably a bridge between the ring atoms 2 and 9 and / or 4 and 5 forms. Annellated aromatic systems such as 2,7-diazaphenanthrene (in the case of only one bridging) or 2,7-diazapyrenium (in the case of two bridges) are among the preferred bispyridinium frameworks used here (cf. 2 ). Nonetheless, derived (fused) heterocyclic compounds can be used in the present invention (see definition of R _a and R _b ). Another exemplary bispyridiumium backbone in which the substituents R _a and R _{b form} a bridge is the tetrahydrodiazapyrene known from [4] (cf. 2 ). For the sake of clarity, it should be said that such systems can of course, as can be seen from the definition of Formula 1, also have a substituent R _c . In one embodiment, R _{c is} preferably halogen, with fluorine again being preferred.

The importance of aryl in the compounds according to formula (I) closes substituted and unsubstituted carbocyclic aromatic groups such as phenyl, naphthyl, anthracyl and heterocyclic aromatic groups such as N-imidazolyl, 2-imidazolyl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 2-pyranyl, 3-pyranyl, 4-pyranyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-pyrazinyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-oxazolyl, 4-oxazolyl and 5-oxazolyl. Ar also includes fused polycyclic aromatic ring systems such as quinoline or 9H-Thioxanthene-10,10-dioxide, which is a carbocyclic aromatic Ring condensed with one or more heterocyclic rings is.

wobei in Formel (Ib)
(mindestens) eine Gruppierung X_a bzw. X_b ersetzt sein kann, die jeweils für ein Heteroatom steht, das aus S, N und O ausgewählt wird, oder für eine Leerstelle steht (d.h. wodurch ein 5-Ring erzeugt wird)
eines oder mehrere der Kohlenstoffatome der beiden Ringssysteme jeweils unabhängig voneinander einen Substituenten R_a bzw. R_b aufweist, der jeweils unabhängig für Alkyl, Aryl, Alkylaryl, Alkenyl, Alkinyl, Halogen, CN, OCN, NCO, COOH, COOR', CONHR', NO₂, OH, OR', NH₂, NHR', NR'R'', SH und SR' steht, wobei R' und R'' unabhängig voneinander Alkyl, Aryl, Alkylaryl, Alkenyl oder Alkinyl sein kann, oder
wobei R_a und R_b zusammen eine Verbrückung zwischen den beiden aromatischen Ringsystemen bildet, die 1 bis 3 Atome umfasst, wobei die Atome unabhängig voneinander aus C, S, N und O ausgewählt werden und durch eine Einfach-, Doppel- oder Dreifachbindung miteinander verknüpft sein können und ferner einen Substituenten R_c aufweisen können, wobei der Substituent R_c die für R_a und Rb, oben angegebene Bedeutung hat,
Y für eine Gruppe steht, die unabhängig voneinander aus CH₂, O, S, NH, NR', COO, CONH, CH=CH, C=C oder Aryl ausgewählt werden kann,
Z_a und Z_b unabhängig voneinander jeweils CH₃, -CH=CH₂, SH, -S-S-,-S(CO)-CH₃, SiCl₃, Si(OR)₃, SiR(OR')(OR''), SiR(OR')₂, Si(R'R'')NH₂, COOH, SO₃, PO₃H, oder NH₂ sein kann,
wobei R' und R'' jeweils unabhängig voneinander Alkyl, Aryl, Arylalkyl, Alkenyl oder Alkinyl sein kann,
wobei n, q jeweils unabhängig voneinander einen Wert zwischen 0 und 12 annehmen können,
j und k jeweils unabhängig voneinander einen Wert zwischen 0 und 6 annehmen können,
p und m jeweils unabhängig voneinander einen Wert zwischen 0 und 12 annehmen können,
wobei die folgenden Verbindungen ausgenommen sind: N,N'-Dimethyl-4,5,9,10-Tetrahydro-2,7-diazapyreniumdiiodid (in [4] beschrieben);
1,1',2,2'-tetramethyl-4,4'-bispyridinium; 1,1',2,-trimethyl-4,4'-bispyridinium (in [5] und [6] beschrieben);
N,N'-Dimethyl-2,7-diazapyrenium (in [7] beschrieben);
N-methyl-N'-(p-toloyl)-2,7-diazapyrenium (in [7] beschrieben);
1,1'-Dimethyl-2-phenyl-6-(p-toloyl)-4,4'-bispyridiumdiperchlorat (in [8] beschrieben);
1,1'-Dimethyl-2-phenyl-4,4'-bispyridiumdiperchlorat (in [8] beschrieben);
6-(Phenyl)-1,1',2-trimethyl-4,4'-bispyridiumdi-perchlorat (in [8] beschrieben);
1,1'-Dimethyl-2-phenyl-6-(2,5-dichloro-3-thienyl)-4,4'-bispyridiumdiperchlorat (in [8] beschrieben).The present invention also relates to new bispyridinium compounds of the general formula (Ib)

where in formula (Ib)
(at least) one group X _a or X _b can be replaced, each of which stands for a heteroatom selected from S, N and O, or stands for a blank (ie which creates a 5-ring)
one or more of the carbon atoms of the two ring systems each independently has a substituent R _a or R _b , each of which is independently for alkyl, aryl, alkylaryl, alkenyl, alkynyl, halogen, CN, OCN, NCO, COOH, COOR ', CONHR' , NO ₂ , OH, OR ', NH ₂ , NHR', NR'R '', SH and SR ', where R' and R '' can independently be alkyl, aryl, alkylaryl, alkenyl or alkynyl, or
where R _a and R _b together form a bridge between the two aromatic ring systems, which comprises 1 to 3 atoms, the atoms being selected independently of one another from C, S, N and O and linked to one another by a single, double or triple bond and can also have a substituent R _c , where the substituent R _{c has} the meaning given above for R _a and Rb,
Y represents a group which can be selected independently of one another from CH ₂ , O, S, NH, NR ', COO, CONH, CH = CH, C = C or aryl,
Z _a and Z _b independently of one another each CH ₃ , -CH = CH ₂ , SH, -SS -, - S (CO) -CH ₃ , SiCl ₃ , Si (OR) ₃ , SiR (OR ') (OR'' ), SiR (OR ') ₂ , Si (R'R'') NH ₂ , COOH, SO ₃ , PO ₃ H, or NH ₂ ,
where R 'and R''can each independently be alkyl, aryl, arylalkyl, alkenyl or alkynyl,
where n, q can independently assume a value between 0 and 12,
j and k can each independently have a value between 0 and 6,
p and m can each independently assume a value between 0 and 12,
except for the following compounds: N, N'-dimethyl-4,5,9,10-tetrahydro-2,7-diazapyrenium diiodide (described in [4]);
1,1 ', 2,2'-tetramethyl-4,4'-bispyridinium; 1,1 ', 2, -trimethyl-4,4'-bispyridinium (described in [5] and [6]);
N, N'-dimethyl-2,7-diazapyrenium (described in [7]);
N-methyl-N '- (p-toloyl) -2,7-diazapyrenium (described in [7]);
1,1'-dimethyl-2-phenyl-6- (p-toloyl) -4,4'-bispyridium diperchlorate (described in [8]);
1,1'-dimethyl-2-phenyl-4,4'-bispyridium diperchlorate (described in [8]);
6- (phenyl) -1,1 ', 2-trimethyl-4,4'-bispyridium di-perchlorate (described in [8]);
1,1'-Dimethyl-2-phenyl-6- (2,5-dichloro-3-thienyl) -4,4'-bispyridium diperchlorate (described in [8]).

Compounds are preferred in which the chain bonded to the nitrogen atom of the respective ring in each case has no more than a total of 20 atoms. Again, connections are ahead moves, in which both chains together have a total length of more than 30 atoms. Expressed with the help of the indices, this means that (j * q + p) or (k * n + m) preferably each independently assume a value (integer) not greater than 20. The sum of (jq + p) + (kn + m) is therefore preferably not greater than 30.

The invention further relates to the Use of bispyridinium compounds of the general formula (I) / (Ib) as a functional component of (electrical) storage units, especially as a functional part of permanent storage.

The representation of bispyridinium compounds according to formula (I) or (Ib) is preferably carried out in stages by first the Bispyridimium unit is synthesized and then the quaternization at the nitrogen atom. Unsubstituted bispyridines can be used in analogy to the biphenyls e.g. using the Ullmann coupling (C-C bond of aryl halides with copper), or Wurtz synthesis (stepwise Implementation with copper, which leads to the formation of asymmetrical connections allowed), see e.g. [9] and those specified there Quotes. The unsubstituted bispyridine is commercially available.

The binding of the N-substituents to the bispyridium unit by simple quaternization with R-X. For the simplest case e.g. by reacting bipyridyl with reagents such as methyl iodide in benzene (see e.g. [10] or [11]). This results in then directly the symmetrically N-substituted Bispyridinium compounds or if a suitable radical X is used gradually unbalanced connections (the choice of X controls solubility in suitable solvents) and is followed by exchange of the counter ion and substitution of the second N atom. In general, this can be formulated as follows.

The substitution on the nitrogen atoms, which leads to asymmetrical connections, e.g. in a two-step reaction take place as described in [12] using the synthesis of N- (n-decyl) -N '- (10-mercaptododecyl) -4,4'-bispyridinium (see also [13] or [14] and [15]).

The substitution of the bispyridinium unit by R _a and R _b , which can be both substituents with electron-donating and electron-withdrawing properties, can be carried out as a preceding reaction as described, for example, in [16], [17] or [18] (cf. in particular [16] Schemes 1 and 2; [17] Compounds 6). Starting from a bispyridinium compound which bears a hydroxyl group in the 2-position (cf. R2 in [17], it is also possible, for example, to form a -SS- or -S- by reaction with P ₂ S ₅ with the formation of a ring System (cf. definition of R _a and R _b ), and, in particular when using 2,7-diazaphenanthrene as the bispyridinium unit, the introduction of the substituents R _a and R _{b can be carried out} analogously to the process described in [19] be carried out (see there in particular compounds 6 and 7).

Connections with (additional) Heteroatoms, i.e. one or more groups X, for example can be obtained by means of the synthesis described in [18] (cf. there blocks 4 and 5).

In the compounds of the formula (I) / (Ib) can the group X as well as the substituents R to influence and targeted control of the electrochemical properties, i.e. in particular the redox potentials of the bispyridinium unit. With such substitutions, the charge balance in one Switching process in the circuit element are supported.

For example, electron-rich substituents R, such as alkyl or aryl residues, which have an inductive, electron-donating effect (the so-called + I effect), facilitate the electron donation by the bispyridinium unit, and thereby reduce the reduction potential. The same applies to substituents which provide lone pairs and enable the formation of mesomeric boundary structures, ie show a + M effect. Examples of such substituents are -OH, -OR, -NH ₂ , -NHR, -SR or fluorine.

Opposing effects, ie the increase in the oxidation potential, can be achieved by substituents with electron-withdrawing -I and -M effects (eg -CN, -NO ₂ , -COOH, -SO ₃ H) or with substituents such as Cl, in which an electron-withdrawing effect unites predominate electron donating effect.

These effects should be derivable and be in good harmony, for example, with trends and findings from photoelectron spectroscopy (see eg [20]). For example, the ionization potential for substituted benzenes is known, which correlates with the energy of the highest occupied molecular orbital (HOMO). + I and + M substituents have higher-energy HOMOs than benzene, ie lower ionization potentials (corresponding to easier oxidizability), in the case of -M or -I substituents the effect is reversed. This influence on the ionization potential is not quite as strong, but it is also clearly present. This relationship should apply above all because the electrophilic aromatic substitution with the reaction-accelerating influence of + M / + I substituents takes place via a primary reaction of the aromatic electron system with E ⁺ , ie it corresponds to an oxidation of the aromatic.

Through the substituent Y can also the electrochemical properties of the bispyridinium compounds used here in the for affects the substituents R and X described above become.

A preferred class of bispyridinium compounds are molecules with long chain alkyl residues. These connections have the advantage that they are training self-organizing layers of redox-active molecules on the surface of the electrically conductive Enable material. For such compounds, j and k in formula (I) take the values 0 on.

In one embodiment, the present inventions molecules preferred, in which the (alkyl) chains located on the pyridine nitrogen atom a length from 6 to 12 atoms. However, it is also possible to use shorter or shorter ones longer Use chains as long as the redox properties of the bispyridinium molecules and the functionality of the circuit element is not affected.

The letter Z in formula (I) stands for one Head or anchor group, by means of which the bispyridinium compounds on the electrically conductive Materials are applied. This immobilization can be done by physical or chemical interactions take place.

These interactions include hydrophobic ones or ionic (electrostatic) interactions and covalent Bindings. For example, when using thiol groups as a substituent and gold as a conductive material based on the Substrate material is applied, the immobilization by the so-called gold-sulfur coupling take place.

If groups such as SH, SiCl ₃ or NH ₂ , COOH are used, the bispyridinium compound can be directly covalently linked to the electrically conductive material. It is also possible to use disulfide compounds (RSSR ', where R = R' = bipyridyl-containing molecule, or R = bipyridyl-containing molecule, and R 'simply methyl or short alkyl), which also form monolayers on gold, however manage through non-covalent interactions. It is also possible, for example, if free hydroxyl groups can be formed on the surface of the electrically conductive material (for example, when using doped silicon), to use alkoxysilanes for the bond, for example -SiR _n (OR ') _{3 – n} with R and R 'alkyl, R' typically methyl or ethyl, n = 0-2).

The covalent link can doing about any suitable linking chemistry respectively. Possible is, however, also a short separate linker for immobilization of the redox-active compounds.

The choice of the respective head group can also be influenced by the type of electrically conductive material. For example, in the case of gold as the conductive material, thiols are particularly suitable as anchor groups; when using palladium, for example, cyanides and isocyanides are preferred head groups and for silicon surfaces are silyl chlorides, silylamines Si (R'R '') NH ₂ and, as above, alkoxysilanes, -SiR ' _n (OR'') _{3 – n} with R 'and R''= alkyl, (typically methyl, ethyl, propyl, butyl etc., n = preferably 0-5, particularly preferably n = 0-2) well-suited anchor groups for immobilization.

Another head group that is generally well suited and therefore also preferred for immobilization is -S (CO) -CH ₃ .

In one embodiment of the circuit element is a covalent link of the redox-active compounds to the first and / or the second conductive Material preferred, because it means the orientation of the molecules and the (Electrical) contact to the conductive materials guaranteed can be.

Below is an electrically inert molecule understood a chemical compound that acts as an electrical insulator serves and is preferably also chemically inert, in particular oxidation or reduction resistant is, and thus the switching process by the redox-active Bispyridinium molecules is not disturbed. Because of their property to serve as an electrical insulator, form the layers of the inert molecules, which consequently also as isolator molecules can denote an isolating matrix to the individual active Areas (positions) of the circuit element from each other electrically to separate.

In principle, any kind of molecules that meet the requirements just mentioned in the circuit element you invention are used. Different types can also be used used by inert molecules to form an insulating matrix.

In a preferred embodiment of the circuit element are the electrically inert molecules compounds with a long chain (saturated) Alkyl.

Preferably, the electrical molecules a head group, by means of which they go out to the first layer can be bound to the electrically insulating substrate material. there is an immobilization over non-covalent or covalent bonds possible. It is possible that inert molecules also on the layer made of the second electrically conductive material to immobilize.

The inert matrix-forming molecules are preferably alkylsilyl compounds of the general formula CH ₃ - (CH ₂ ) _p -SiR ₁ R ₂ R ₃ (II) where in formula (II) p is an integer between 1 and 30, preferably 1 and 20, and wherein the inert molecules have at least one of the radicals R ₁ , R ₂ and R ₃ , which are independently hydrogen, halogen, OR ', NHR', NR'R '', where R 'and R''is alkyl (typically methyl, ethyl, propyl, butyl etc., n = preferably 0-5, particularly preferably n = 0-2) , are immobilized on the first layer. Such compounds are commercially available, for example from ABCR / Gelest (simpler compounds also from Fluka or Aldrich). These compounds are particularly preferred when a silicon-based substrate is used. In this case, the inert insulator molecules are covalently bound via free hydroxyl groups on the surface of the substrate material.

At this point it should be noted that the length of the alkyl chains of the electrically inert molecules of the respectively selected bispyridinium compounds depends. Its cheap, if the length of the molecules nearly is the same, so close to achieve equal thicknesses of the monomolecular layers. The number of the alkyl units in the isolating tail group of the inert Insulator molecules can be estimated from the known bond lengths. However, a purely empirical procedure for determining the most suitable molecular length possible.

Hence the use of electrical inert molecules with a long-chain alkyl radical, especially of alkylsilyl compounds of the formula (II) in circuit elements is another subject of Invention.

In one embodiment, this is here circuit element disclosed an element in which a plurality of discrete Areas of the first electrically conductive material in the substrate material is embedded and / or applied to the substrate material. This Design enables it, for example, the circuit element of the invention as an electrical Form memory with a plurality of memory cells.

In this context, be on it pointed out that it goes without saying possible is, both different bispyridinium compounds on one to apply a single discrete area of the conductive first material. It is also possible different of these areas with different redox-active compounds to thereby provide the properties of the circuit element adapt to a specific purpose.

In a preferred embodiment of the circuit element is the first electrically conductive material Gold, silver, palladium, platinum or silicon. The discrete area the first conductive Ingesting material can be configured as an electrode in the substrate material his.

In another embodiment of the Circuit element disclosed here has the layer of the second electrically conductive Material preferably titanium and / or aluminum. The second layer can also be designed as an electrode. In addition, as others Materials for forming the second electrode, the materials suitable for the first electrode.

In a preferred embodiment is the circuit element described here between two electrodes arranged. These electrodes can the first and the second electrically conductive material. In this Design, i.e. when arranged between two electrodes the circuit element of the present invention is a changeable Resistance and therefore a storage element.

In a training course where one Variety of redox active bispyridinium layers is used forms an arrangement of such memory elements, a memory matrix, i.e. it can be used as an electrical storage. On The advantage of this configuration is the use of a molecular one Bipolar as a storage element, which makes it different from conventional storage elements how RAMs reduce the wiring effort and the packing density elevated becomes. Thus, the memory element of the invention provides access to a highly integrable electrical storage. The storage element is preferably a permanent storage element and that on a A plurality of storage elements based electrical storage is preferred a permanent storage. Such permanent storage can e.g. as Memory for graphic information is used, for example as a memory for "on-chip" video films.

In the method of the invention for Manufacturing a circuit element is first a first layer submitted an insulating substrate material and a first electrical conductive Material in at least one discrete position in the substrate material embedded and / or applied to the substrate material.

Thereafter, redox-active bispyridinium molecules as a monomolecular layer on the at least immobilized a discrete area made of the first electrically conductive material. Thereupon, electrically inert molecules are immobilized on the first layer made of the electrically insulating substrate material. As a result, the electrically inert molecules form a matrix which surrounds the at least one region with the monomolecular layer of bispyridinium molecules.

Then in the process a second layer with a second electrically conductive material applied to the layer of the electrically inert molecules and the bispyridinium molecules. This causes the bispyridinium molecules to enter the monomolecular Layer with the second electrically conductive material of the second Layer in contact. The inert matrix-forming isolator molecules do not have to on the second conductive Material to be immobilized.

In a preferred embodiment however, the bispyridinium compounds are also on the second electrically conductive Material immobilized to make electrical contact with this material to ensure. This immobilization can be due to the identical head group Z in the same way as the immobilization on the first conductive material respectively.

The method is preferred as bispyridinium molecules compounds of the general formula (I) used. As electrically inert molecules preferably compounds with a long-chain alkyl radical, in particular Compounds according to formula (II) used.

The first conductive material is preferred Gold used. Furthermore, the first electrically conductive material preferably in a regular arrangement embedded and / or applied in the substrate material.

Applying the layer from the second electrical material is preferably done in that the second electrical material on the layer of the electrically inert molecules and the bispyridinium molecules is evaporated.

In a further embodiment of the The method is titanium and / or the second electrically conductive material Aluminum used.

Embodiments of the invention are shown in the figures and are explained in more detail below.

Show it

1a and 1b the redox-active bispyridinium unit of the molecules used in the inventions and a schematic representation of the operation of a circuit element of the invention;

2a to 2e Formula representations of redox-active bispyridinium compounds preferably used in the invention and preferably used electrically inert molecules;

3a to 3e an embodiment of the method described here for producing a circuit element;

4a to 4c an electrical memory in which the circuit elements described here are used, and its mode of operation.

1a shows a formula and a schematic representation of the bispyridinium unit, by means of which the redox process of the bispyridinium unit (of the bispyridinium backbone) taking place at the molecular level is illustrated.

The double positively charged cation 101 , which is the reference number in the diagram 102 is the species that is not conductive below a given reduction potential.

The cation is above this predetermined reduction potential 101 represents an electron acceptor. When an electron is taken up, the doubly positively charged cation changes to a single positively charged radical cation 103 ( 104 in the schematic representation). The free cation makes the radical cation electrically conductive. This state is below the oxidation potential of the radical cation 103 in front. The radical cation thus represents an electron donor above the oxidation potential 105 labeled alkyl chains, which are bonded to the pyridine ring system via the nitrogen atom of the respective ring, do not take part in the redox process per se, but rather act as an insulator. However, substituents built into the alkyl chains, as described above, can influence the position of the redox potential, for example by + M and / or + I effects.

1b shows schematically the potential relationships and mode of operation (the switching principle) of a circuit element configured as a memory element of the present invention. This memory element can be a circuit element in which the one area made of the first electrically conductive material and the layer made of the second electrically conductive material is designed as an electrode.

When creating small positive or negative potentials 107 (the potential is on the x-axis 106 displayed in its relative position), no changes in the redox state are yet initiated. This area 108 is used to read the memory cell. The creation of a larger negative potential 109 causes a reduction of the molecule (transition to radical cation 104 ). This area 110 is used to describe the storage element. Becomes a bigger positive potential 111 applied to the storage element, this causes an oxidation of the molecule, ie a conversion into the dication 102 , This one with the potential 111 beginning area 112 is used to delete the storage element. Since this re dox process is reversible, any number of write, read and delete operations can be performed.

2a shows bispyridinium compounds 201 according to formula (I), which are preferably used in the present invention. 2 B to 2d show 2,7-diazaphenanthrene ( 205 ), 2,7-diazapyrenium ( 206 ) and tetrahydrodiazapyrene ( 207 ) as examples of a bispyridiumium backbone in which the substituents R _a and R _{b form} a bridge. In 2e is in the formula and schematically a trichloroalkylsilane compound 202 shown, which represent a preferred embodiment of the electrically inert insulator molecules. The head or anchor group for immobilization has the reference symbol 203 and the long chain (isolating) alkyl chain the reference number 204 ,

3 illustrates an example of the method of manufacturing a circuit element described here 300 ,

3a shows the substrate material 301 in which discrete areas 302 . 303 . 304 are arranged from the first electrically conductive material. The substrate material is an insulator material such as silicon oxide. The discrete areas 302 . 303 . 304 are made of gold.

Then on the areas 302 . 303 . 304 a redox active bispyridinium compound 305 immobilized ( 3b . 3c ), with a monomolecular layer of the molecules of the compound on each of these areas 305 is formed. The compound here is N, N-di- (1.0-mercaptodecyl) -4,4'-bispyridinium dibromide, which can be synthesized as described in [15]. Immobilization on the gold surfaces of the areas 302 . 304 . 304 therefore takes place via the gold-sulfur coupling (see detailed view in 3c ). For this purpose, the bispyridium compound is usually taken up in an organic solvent such as hexane or ethanol (depending on the solubility) in a concentration of 10 to 100 mM and brought into contact with the substrate surface. The adsorption then usually takes place in a period of 30 minutes to about 12 hours (overnight) at room temperature. Then the surface is rinsed carefully with solvent. The substrates thus provided with the monomolecular layers are stable in air and solvent (if the temperature is not too high). [21]) provides an overview of the immobilization methods that can be used here.

After that, electrically inert molecules 306 on the layer of substrate material 301 immobilized as a monomolecular layer ( 3d ). As molecules 306 Trichloralkylsilanes or alkoxysilanes with an alkyl chain length of about 10 to 30, preferably with up to about 20 carbon atoms are used here. The immobilization takes place via covalent bonds of the silicon atom with hydroxyl groups on the surface of the substrate material 301 silicon dioxide used.

In the next step, the second electrically conductive layer is formed 307 of the circuit element ( 3e ). To do this, first create a layer 308 made of titanium on the monomolecular layers of the bispyridinium compounds 305 and the isolator molecules 306 evaporated under vacuum. Then another layer 309 evaporated from aluminum under vacuum. In principle, all methods can be used to apply the second electrical layer, which enable a gentle deposition of the metal layer.

In this way, a circuit element formed with a plurality of molecular resistors that are e.g. can be used as part of a memory cell.

4 shows a section of an electrical permanent memory 400 of the present invention, which is based on a large number of the circuit elements described here (cf. 4c ).

The permanent storage 400 has a substrate 401 made of an insulator material in which a variety of discrete areas 402 are formed from a first conductive material. The substrate / insulator material is silicon dioxide, the first conductive material is gold. The discrete areas are made of gold with an electrical connection 403 provided, ie designed as an electrode. In the fields 402 gold is a monomolecular layer of redox-active bispyridinium compounds 404 immobilized. As a connection 404 N- (n-decyl) -N '- (10-mercaptododecyl) -4,4'-bispyridinium is used here, which is obtained according to [12]. Alternatively, the compounds described in [13] and [14] can also be used.

On the substrate material 401 is a layer of alkyltrichlorosilane compounds as electrically inert insulator molecules 405 immobilized. In the present case, octadecyltrichlorosilane, C ₁₈ H ₃₅ SiCl ₃ (commercially available, for example, from Aldrich) is used for this.

The two molecular layers are in contact with a second layer 406 made of electrically conductive material that has been applied to the molecular layers. The second layer 406 has a layer 407 made of titanium and a layer 408 made of aluminium. It is also with an electrical connection 409 provided and thus designed as an electrode.

4a and 4b show the process of storing information through the memory 400 , To a selected layer of the redox-active bispyridinium compounds 404 for example via the electrical connection 403 (and the area designed as an electrode 402 ) applied a negative potential that is greater than the reduction potential of the bispyridinium compounds. This leads to a voltage (write voltage) on the electrodes 403 . 409 and to a write operation in that each bispyridinium unit has one electron over the range 402 absorbs and into the form of the simply positively charged radical cation goes (cf.

1b ).

The deletion process, which is also part of information storage does the following yourself.

To a selected layer of the redox-active bispyridinium compounds 404 is again, for example, via the electrical connection 403 a positive potential that is greater than the oxidation potential of the bispyridinium compounds. This is with a voltage (erase voltage) on the electrodes 403 . 409 and an extinguishing process in which each bispyridinium unit transfers an electron by means of the region (the electrode) while changing into the double positively charged dication. 402 emits.

In this context, it should be noted that the permanent memory 400 as well as in all other configurations that use a large number of separate circuit elements of the invention, each circuit or memory element can be individually controllable / addressable.

The reading process is in 4c illustrated. In this process, a so-called read voltage is applied, which indicates the redox state of the bispyridinium compounds 404 , as it currently exists in the individual memory elements, is not influenced. This means that the applied potential difference does not cause an oxidation or a reduction of the bispyridinium molecules in the individual separate storage elements. The read voltage leads to a current flow through each storage element (through the arrows 410 symbolized), the size of which is determined by the respective state of charge in the storage elements, and which is used for further information processing.

In the case of molecular layers in which the bispyridinium molecules as dication little or no current is measured. For layers in which the bispyridinium units of the molecules are considered simple positively charged radical cation, a (larger) current flow measured.

The permanent storage 400 thus represents a small, scalable and addressable memory, the design of which is considerably simplified compared to conventional memories such as DRAMs or SRAMs and, for example, requires less wiring.

• [1] C. P. Collier et al., Electronically configurable molecular-based logic gates, Science, Vol. 285, S. 391– 394, 1999
• [2] C.P. Collier et al., A [2]Catenane-based solid state electronically reconfigurable switch, Science, Vol. 289, S. 1172–1175, 2000
• [3] D.I. Gittins et al., A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups, Nature, Vol. 408, S. 67–69, 2000
• [4] Kawashima et al., The synthesis and properties of a methylviologen analogue, Tetrahedron Letters, Vol. 25, Nr. 25, S. 1585–1586, 1984
• [5] JP 56118002
• [6] JP 57014507
• [7] A. J. Blacker et al. Molecular Anion Binding and Substrate Photoxidation in Visible Light by 2,7-Diazapyrenium Cations, Helvetica Chimica Acta, Vol. 70, S. 1–12, 1987
• [8] R. Bauer et al., Synthesis and electrochemical properties of some new bipyridinium and related compounds Z. Naturforsch., B: Chem. Sci. 43 (4), S. 475– 482, 1988
• [9] J. March, Advanced Organic Chemistry, 3. Auflage (Wiley, New York, 1985), S. 597ff
• [10] P. Stehle et al. Isotachophoresis of quarternary 4,4'-Bipyridylium Salts – Analytical Control of synthesis and purification procedures, J. Chromatogr. 449(1), 299–305, 1988
• [11] Blacker et al., Molecular anion binding and substrate photooxidation in visible light by 2,7-diazapyrenium cations, Helvetica Chimica Acta, 70, S. 1–12, 1987
• [12] H. C. DeLong & D. A. Buttry, Ionic Interaktions play a major role in determining the electrochemical behavoir of self-assembling viologen monolayers, Langmuir, 6, S. 1319–1322,1990
• [13] X. Tang et al., A vibrational spectroskopic study of the structure of electroactive self-assembled monolayers of viologen derivatives; Langmuir, 10, S. 2235–2240, 1994
• [14] H. C. DeLong & D. A. Buttry, Environmental Effects on redox potential of viologen groups in electroactive self-assembling viologen monolayers, Langmuir, 8, S. 2491–2496, 1992
• [15] D. I. Gittins et al., Diode-like electron transfer accross nanostructured films containing a redox ligand, J. Mater. Chem., Vol. 10, S. 79–83, 2000
• [16] R. Bauer, Rupert et al, On the synthesis and electrochemical properties of some new bipyridium and related compounds, Z. Naturforsch., B: Chem. Sci. 43 (4), S. 475–82, 1988
• [17] E. V. Dehmlow & A. Sleegers, Synthesen von hydroxilierten Bipyridinen, III: Synthese von unsymmetrischen und symmetrischen Dihydroxybipyridinen, Liebigs Ann. Chem. 9, S. 953–959, 1992
• [18] H. Fischer & A. L. Summers, Synthesis, polarography and herbicidal activity of quaternary salts of 2-(4-pyridyl)-1,3,5-triazines, 5-(4-pyridyl)pyrimidine, 2-(4-pyridyl)pyrimidine and related compounds, J. Heterocycl. Chem. 17 (2), S. 333–336, 1980
• [19] E. W. Gill & A. W. Bracher, The synthesis and characterisation of some diazaphenanthrene derivatives, J. Heterocyclic Chem. 20, S. 1107–1109, 1983
• [20] D. W. Turner, Molecular Photoelectron Spectroscopy, Wiley, London, 1970
• [21] A. Ulman, Formation and Structure of Self-Assembled Monolagers, Chem. Rev., vol 96 (4), 1533–1554 (1996).

The following publications are cited in this document:

• [1] CP Collier et al., Electronically configurable molecular-based logic gates, Science, vol. 285, pp. 391-394, 1999
• [2] CP Collier et al., A [2] Catenane-based solid state electronically reconfigurable switch, Science, Vol. 289, pp. 1172-1175, 2000
• [3] DI Gittins et al., A nanometer-scale electronic switch consisting of a metal cluster and redox-addressable groups, Nature, Vol. 408, pp. 67-69, 2000
• [4] Kawashima et al., The synthesis and properties of a methylviologen analogue, Tetrahedron Letters, Vol. 25, No. 25, pp. 1585-1586, 1984
• [5] JP 56118002
• [6] JP 57014507
• [7] AJ Blacker et al. Molecular Anion Binding and Substrate Photoxidation in Visible Light by 2,7-Diazapyrenium Cations, Helvetica Chimica Acta, Vol. 70, pp. 1-12, 1987
• [8] R. Bauer et al., Synthesis and electrochemical properties of some new bipyridinium and related compounds Z. Naturforsch., B: Chem. Sci. 43 (4), pp. 475-482, 1988
• [9] J. March, Advanced Organic Chemistry, 3rd edition (Wiley, New York, 1985), pp. 597ff
• [10] P. Stehle et al. Isotachophoresis of quarternary 4,4'-bipyridylium Salts - Analytical Control of synthesis and purification procedures, J. Chromatogr. 449 (1), 299-305, 1988
• [11] Blacker et al., Molecular anion binding and substrate photooxidation in visible light by 2,7-diazapyrenium cations, Helvetica Chimica Acta, 70, pp. 1-12, 1987
• [12] HC DeLong & DA Buttry, Ionic Interactions play a major role in determining the electrochemical behavior of self-assembling viologen monolayers, Langmuir, 6, pp. 1319-1322, 1990
• [13] X. Tang et al., A vibrational spectroscopic study of the structure of electroactive self-assembled monolayers of viologen derivatives; Langmuir, 10, pp. 2235-2240, 1994
• [14] HC DeLong & DA Buttry, Environmental Effects on redox potential of viologen groups in electroactive self-assembling viologen monolayers, Langmuir, 8, pp. 2491-2496, 1992
• [15] DI Gittins et al., Diode-like electron transfer accross nanostructured films containing a redox ligand, J. Mater. Chem., Vol. 10, pp. 79-83, 2000
• [16] R. Bauer, Rupert et al, On the synthesis and electrochemical properties of some new bipyridium and related compounds, Z. Naturforsch., B: Chem. Sci. 43 (4), pp. 475-82, 1988
• [17] EV Dehmlow & A. Sleegers, Syntheses of Hydroxilated Bipyridines, III: Synthesis of Unsymmetrical and Symmetrical Dihydroxybipyridines, Liebigs Ann. Chem. 9, pp. 953-959, 1992
• [18] H. Fischer & AL Summers, Synthesis, polarography and herbicidal activity of quaternary salts of 2- (4-pyridyl) -1,3,5-triazines, 5- (4-pyridyl) pyrimidines, 2- (4- pyridyl) pyrimidine and related compounds, J. Heterocycl. Chem. 17 (2), pp. 333-336, 1980
• [19] EW Gill & AW Bracher, The synthesis and characterization of some diazaphenanthrene derivatives, J. Heterocyclic Chem. 20, pp. 1107-1109, 1983
• [20] DW Turner, Molecular Photoelectron Spectroscopy, Wiley, London, 1970
• [21] A. Ulman, Formation and Structure of Self-Assembled Monolagers, Chem. Rev., vol 96 (4), 1533-1554 (1996).

101

Di-cation the bispyridinium unit

102

Di-cation the bispyridinium unit

103

simple positively charged radical cation

104

simple positively charged radical cation

105

alkyl chains

106

X axis

107

small positive or negative potentials

108

to the Read the memory element used area

109

bigger negative potential

110

to the Describe the memory element used

Area

111

bigger positive potential

112

to the Clear of the memory element used area

201

Bispyridinium connections

202

Trichloralkylsilanverbindung

203

head group

204

long chain alkyl chain

205

2,7-diazaphenanthrene

206

2,7-diazapyrenium

207

Tetrahydrodiazapyren

300

circuit element

301

substrate material

302

Area of gold

303

Area of gold

304

Area of gold

305

Bispyridinium connection

306

inert molecules

307

second electrically conductive layer

308

layer made of titanium

309

layer made of aluminium

400

permanent memory

401

substratum made of insulator material

402

discreet Gold areas

403

electrical connection

404

redox-active Bispyridinium connections

405

insulator molecules

406

second Layer of electrically conductive material

407

layer made of titanium

408

layer made of aluminium

409

electrical connection

410

arrow

Claims (21)

Circuit element with a first layer of an electrically insulating substrate material, - with a first electrically conductive material, which is designed as at least one discrete area such that it is embedded in the substrate material and / or is applied to the substrate material, - a second layer with a second electrically conductive material, and - a monomolecular layer of redox-active bispyridinium molecules, which is arranged between the first layer of the electrically insulating substrate material and the second layer with the second electrically conductive material, the bispyridinium molecules of the monomolecular layer the electrically conductive material formed as at least one discrete region are immobilized, and wherein bispyridinium molecules of the monomolecular layer with the second electrical material of the second layer are in electrical contact, and - in which electrically inert molecules are immobilized on the first layer made of the electrically insulating substrate material, which form a matrix which surrounds the at least one discrete region with the monomolecular layer made of bispyridinium molecules. Circuit element according to Claim 1, in which the bispyridinium molecules are compounds of the general formula (I),

in formula (I) one or more of the carbon atoms of the two aromatic ring systems of the bispyridinium unit can be replaced independently of one another by at least one group X _a or X _b , each of which represents a heteroatom selected from S, N and O. is, or stands for a blank, one or more of the carbon atoms of the two ring systems can each independently have a substituent R _a or R _b , each independently for alkyl, aryl, alkylaryl, alkenyl, alkynyl, halogen, CN, OCN , NCO, COOH, COOR ', CONHR', NO ₂ , OH, 0R ', NH ₂ , NHR', NR'R '', SH and SR ', where R' and R '' independently of one another are alkyl, aryl, Can be alkylaryl, alkenyl or alkynyl, or where R _a and R _b together can form a bridge between the two aromatic ring systems, which comprises 1 to 3 atoms, the atoms being selected independently of one another from C, S, N and O and by a single, double or triple bin dung may be linked to one another and may furthermore have a substituent R _c , where the substituent R _{c has} the meaning given above for R _a and R _b , Y stands for a group which, independently of one another, consists of CH ₂ , O, S, NH, NR ', COO, CONH, CH = CH, C = C or aryl can be selected, Z _a and Z _b independently of one another each CH ₃ , -CH = CH ₂ , SH, -SS-, -C (CO) CH ₃ , SiC1 ₃ , Si (OR) ₃ , SiR (OR ') (OR''), SiR (OR') ₂ , Si (R'R '') NH ₂ , COOH, SO ₃ , PO ₃ H, or NH ₂ can be, where R 'and R''can each independently be alkyl, aryl, arylalkyl, alkenyl or alkynyl, where n, q can each independently take on a value between 0 and 12, j and k each independently of one another can assume between 0 and 6, p and m can each independently assume a value between 0 and 12. Circuit element according to claim 1 or 2, wherein the electrical inert molecules Are compounds with a long chain alkyl radical. The circuit element of claim 3, wherein the inert molecules are one Have head group, by means of which they covalently to the first layer are bound from the electrically insulating substrate material. Circuit element according to Claim 4, in which the inert molecules are alkylsilyl compounds of the general formula CH ₃ - (CH ₂ ) _p -SiR ₁ R ₂ R ₃ (II) where in formula (II) p is an integer between 1 and 30, preferably 1 and 20, and where R ₁ , R ₂ and R _{3 are} independently hydrogen, halogen, OR ', NHR', NR'R ''can be, where R' and R '' is alkyl. Circuit element according to one of the preceding claims, which a plurality of discrete areas from the first electrically conductive Material embedded in the substrate material and / or on the substrate material is applied. Circuit element according to one of the preceding claims, which is the first electrically conductive material Gold, silver is palladium, platinum or silicon. Circuit element according to one of the preceding claims, wherein the layer of the second has electrically conductive material titanium and / or aluminum. Circuit element according to one of the preceding claims, which the first electrically conductive material and the second electrically conductive material are designed as electrodes. Circuit element according to claim 9, which is a memory element. Circuit element according to claim 10, which is a permanent memory is. Method for producing a circuit element, in which - a layer is made of an insulating substrate material, - a first electrically conductive Material in at least one discrete position in the substrate material is embedded and / or applied to the substrate material, - redox active Bispyridinium molecules as a monomolecular layer on the at least one discrete area from the first electrically conductive Material to be immobilized - Electrically inert molecules on the first layer of the electrically insulating substrate material be immobilized, which makes the electrically inert molecules a Form matrix, which has the at least one area with the monomolecular Layer of bispyridinium molecules surrounds, - one second layer with a second electrically conductive material applied to the layer of the electrically inert molecules and the bispyridinium molecules is what causes the bispyridinium molecules of the monomolecular layer in contact with the second electrical material of the second layer to step. A method according to claim 12, in which as bispyridinium molecules compounds of the general formula (I) can be used. A method according to claim 12 or 13, in which as electrically inert molecules Compounds with a long chain alkyl radical can be used. Method according to one of claims 12 to 14, in which as first conductive Material gold is used. Method according to one of claims 12 to 15, wherein the first electrically conductive Material in a regular arrangement is embedded and / or applied in the substrate material. Method according to one of claims 12 to 16, wherein the second electrical material on the layer of the electrically inert molecules and evaporated the bispyridinium molecules becomes. The method of claim 17, wherein the second is electrical conductive material titanium and / or aluminum is used. Bispyridinium compounds of the general formula (Ib)

wherein in formula (Ib) one or more of the carbon atoms of the two aromatic ring systems of the bispyridinium unit can be replaced independently of one another by at least one group X _a or X _b , each of which represents a heteroatom selected from S, N and O. or a vacancy is one or more of the carbon atoms of the two ring systems each independently of one another has a substituent R _a or R _b which each independently represents alkyl, aryl, alkylaryl, alkenyl, alkenyl, halogen, CN, OCN, NCO, COOH, COOR ', CONHR', NO ₂ , OH, OR ', NH ₂ , NHR', NR'R '', SH and SR ', where R' and R '' are independently alkyl, aryl, alkylaryl, alkenyl or can be alkynyl, or where R _a and R _b together form a bridge between the two aromatic ring systems, which comprises 1 to 3 atoms, the atoms being selected independently of one another from C, S, N and O and by a simple, Double or triple bond with each other r can be linked and also a sub may have substituents R _e , where the substituent R _{c has} the meaning given for R _a and R _b above, Y stands for a group which independently of one another from CH ₂ , O, S, NH, NR ', COO, CONH, CH = CH, C = C or aryl can be selected, Z _a and Z _b independently of one another each CH ₃ , -CH = CH ₂ , SH, -SS-, SiCl ₃ , Si (OR) ₃ , SiR (OR ') ( OR ''), SiR (OR ') ₂ , Si (R'R'') NH ₂ , Si (R ₂ ') NH ₂ , COOH, SO ₃ , PO ₃ H, or NH ₂ , where R ' and R ″ can each independently be alkyl, aryl, arylalkyl, alkenyl or alkynyl, where n, q can each independently take a value between 0 and 12, j and k can each independently take a value between 0 and 6, p and m can each independently take a value between 0 and 12, with the exception of the following compounds: N, N'-dimethyl-4,5,9,10-tetrahydro-2,7-diazapyrenium diiodide; 1,1 ', 2,2'-tetramethyl-4,4'-bispyridinium; 1,1 ', 2-trimethyl-4,4'-bispyridinium; N, N'-dimethyl-2,7-diazapyrenium; N-methyl-N '- (p-toloyl) -2,7-diazapyrenium, 1,1'-dimethyl-2-phenyl-6- (p-toloyl) -4,4'-bispyridium diperchlorate; 1,1'-dimethyl-2-phenyl-4,4'-bispyridiumdiperchlorat; 6- (phenyl) -1,1 ', 2-trimethyl-4,4'-bispyridiumdi perchlorate; 1,1'-dimethyl-2-phenyl-6- (2,5-dichloro-3-thienyl) -4,4'-bispyridiumdiperchlorat; Use of bispyridinium compounds of the general formula (I) or (Ib) as a functional unit in storage units. Use of electrically inert molecules with a long chain alkyl radical in circuit elements.